N-monosubstituted indoanilines as dyestuffs for keratinic fibers

ABSTRACT

New dyestuffs are described for keratinic fibers which produce particularly luminous shades without the need for an oxidizing agent. These dyestuffs have the formula: ##STR1## or a tautomeric form thereof wherein each of R 1  and R 4 , which may be identical or different, represents a member selected from hydrogen, halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, acylamino and ureido; 
     Each of R 2  and R 3 , which may be identical or different, represents a member selected from hydrogen, halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, amino, N-alkylamino, N-(hydroxyalkyl)-amino, N-(carbamyl-alkyl)-amino, acylamino and ureido, each of said alkyls containing 1 to 6 carbon atoms; 
     Each of R 5  and R 6 , which may be identical or different, represents a member selected from hydrogen, halogen, alkyl containing 1 to 6 carbon atoms and alkoxy containing 1 to 6 carbon atoms, with the proviso that when R 5  and R 6  are both other than hydrogen at least one is in a meta-position relative to the NHR 7  group; and R 7  represents a member selected from alkyl, hydroxyalkyl, acylaminoalkyl, mesylaminoalkyl, carbamylalkyl, aminoalkyl, piperidinoalkyl and morpholinoalkyl, each of said alkyls containing 1 to 6 carbon atoms.

The present invention relates to indoanilines in which the amino group in the 4'-position is monosubstituted.

It is known to dye keratin fibers, more particularly living human hair, by applying to the hair, in the presence of an oxidizing agent such as hydrogen peroxide, added at the time of use, a dyeing composition comprising a mixture, in a suitable cosmetic carrier, of compounds belonging to each of two categories. The first category of compounds, generally called "oxidation bases", comprises mainly para-phenylene-diamines or para-amino-phenols which lead, on oxidation, to para-benzoquinonediimines or to para-benzoquinone-monoimines. The second category of compounds, generally called "coupling agents", comprises meta-amino-phenols, meta-acetylamino-phenols, meta-diamines and meta-diphenols. They are compounds with which the benzoquinonemono or di-imines will react to give rise to dyestuffs called, depending on their structure, indophenols, indoanilines or indamines.

These dyestuffs, from which a range of exceptionally rich shades can be obtained, are primarily noted for the luminous nature and for the rich sheen attainable therewith. However, when a complex dyeing composition is used, that is to say a composition which comprises several bases and several coupling agents, it is often very difficult to predict the contribution which each possible combination of oxidation base and coupling agent will make to the final shade. In other words, firstly, it is very difficult at the start to make an exact prediction as to the final shade, and, secondly, for a given dyeing composition, it is not often easy to be certain of perfect reproducibility. These difficulties are increased by the fact that various side reactions change the final shade. Examples of such side reactions are the formation of compounds of the Bandrowsky base type from the oxidation bases, the recondensation of a molecule of oxidation base with certain indophenols or with certain indoanilines or indamines and the formation of quinones.

An object of the present invention is to provide a process for dyeing keratin fibers, and particularly living human hair, which does not require the addition of an oxidizing agent at the time of use. The present invention also relates to the dyes and dye compositions for use in said process.

The objects of the present invention can be achieved by using certain novel indoanilines which possess the advantage of being able to give a very particularly rich range of extremely luminous shades of excellent aesthetic quality.

It has been found that by varying the nature of the substituent in the 4'-position it is possible to change various characteristics of such dyes, in particular their solubility, affinity and compatibility. Thus, increased solubility can be achieved by introducing a hydroxyalkyl or sulphoalkyl substituent, while the solubility of the dye in an alkaline medium can be improved by introducing a mesylaminoalkyl substituent. The affinity of the dye for keratin fibers can be increased by introducing an aminoalkyl substituent.

The present invention provides a N-monoalkyl-amino-indoaniline of the formula (I) ##STR2## wherein each of R₁ and R₄, which may be identical or different, represents hydrogen, halogen, lower alkyl, lower alkoxy, acylamino or ureido;

each of R₂ and R₃, which may be identical or different, represents hydrogen, halogen, lower alkyl, lower alkoxy, amino, N-(lower alkyl)-amino, N-[hydroxy-(lower alkyl)]-amino, N-[carbamyl-(lower alkyl)]-amino, acylamino or ureido;

each of R₅ or R₆, which may be identical or different, represents hydrogen, halogen, lower alkyl or lower alkoxy, with the proviso that R₅ and R₆ can occupy any two free positions but when they are both other than a hydrogen, at least one of the two occupies a meta-position relative to the --NHR₇ group; and

R₇ represents unsubstituted lower alkyl or substituted lower alkyl, and in particular hydroxy-(lower alkyl), acylamino-(lower alkyl), mesylamino-(lower alkyl), carbamyl(lower alkyl), amino-(lower alkyl), piperidino-(lower alkyl) or morpholino(lower alkyl).

By "lower" alkyl or "lower" alkoxy is meant alkyl or alkoxy containing 1 to 6, preferably 1 to 4, carbon atoms.

The invention also relates to the tautomeric form of the compounds of formula (I), especially those of the formula ##STR3## or in the case where R₃ denotes an optionally mono-substituted amino group, those of the formula ##STR4## wherein R represents hydrogen, lower alkyl, hydroxy-(lower alkyl) or carbamyl-(lower alkyl).

The compounds of this invention can be prepared by condensing a compound of the formula: ##STR5## or an addition salt thereof, on a phenolic compound of the formula ##STR6## or an addition salt thereof.

In formula (IV), Z represents --NH₂ or --NO. When Z denotes --NH₂, R₁ to R₇ are as defined above for formula (I). When Z denotes --NO, R₁ to R₆ are as defined above for formula (I) and R₇ represents unsubstituted lower alkyl.

When Z denotes --NH₂, the condensation is suitably carried out in an aqueous, aqueous-alcoholic or aqueous-acetone medium, at an alkaline pH generally greater than 8 and in the presence of an oxidizing agent, for example, ammonium persulphate, potassium ferricyanide or hydrogen peroxide. Generally the alkaline pH is obtained with ammonia or with an alkaline carbonate preferably sodium carbonate and the reaction is carried out at a temperature from about 0° to 25° C.

When Z denotes -NO, the condensation is generally carried out at a temperature of about 50° C, in an aqueous-ethanolic medium which is neutral or has been rendered alkaline by adding a dilute solution of a base preferably sodium hydroxide.

The present invention also provides a dyeing composition for keratin fibers, and particularly for living human hair, which contains in a compatible vehicle, usually an aqueous or aqueous-alcoholic solution, at least one compound of the present invention.

These dyeing compositions generally contain 0.001 to 2% of compound of formula (I), relative to the total weight of the composition.

The dyeing composition according to this invention can contain the idoanilines of formula (I) as the only dyestuff. It is, however, possible to mix the dyestuffs of this invention with other dyestuffs usually employed for dyeing hair, for example nitrobenzene, azo, anthraquinone, indamine, indophenol and/or other indoaniline dyestuffs. Generally when a dye other than the dye of the present invention is employed, the said other dye or dyes is present in amounts of about 0.001 to 1 percent by weight of said composition.

The compositions according to the present invention are generally in the form of an aqueous or aqueous-alcoholic solution containing one or more compounds of formula (I), which may or may not be mixed with other dyestuffs. They can however also contain, for example, thickeners and be in the form of creams or gels. Suitable thickeners which can be used include cellulosic derivatives such as methyl-cellulose, hydroxyethyl-cellulose and carboxymethyl-cellulose; acrylic polymers such as the sodium salt of polyacrylic acid and ethanolamides of fatty acids, preferably mono- or diethanolamide of fatty acids of copra and carboxyvinyl polymers. The thickener can be present, for instance, in amounts of about 0.5 to 7 percent by weight of said composition.

The dyeing composition can contain, as solvents, water, lower alkanols, for example ethanol or isopropanol, and polyhydric alcohols such as glycols, for example ethylene glycol, propylene glycol, butyl glycol, diethylene glycol and the monomethyl ether of diethylene glycol. The solvent is generally present in amounts of about 1 to 60 percent by weight of said composition.

The compositions can also contain various adjuvants usually employed in cosmetics for the hair, such as wetting agents, for example oxyethylenated alkylphenols and oxyalkylenated fatty alcohol sulphates and sulphonates, dispersing agents, swelling agents, penetrating agents, softeners or perfumes. They can, moreover, be packaged in aerosol containers in the presence of a propellant gas. Suitable propellant gases include nitrogen, nitrous oxide, volatile hydrocarbons such as butane, isobutane or propane, or, preferably, fluorinated hydrocarbons (sold under the name of "Freon") such as dichloridifluoromethane, 1,1-difluoro-methane, 1,2-dichloro-1,1,2,2-tetrafluoro-ethane or 1-chloro-1,1-difluoro-methane; mixtures of two or more hydrocarbons or fluorinated hydrocarbons can also be used.

The pH of the compositions, which can vary within wide limits, is generally from about 5 to 11 and preferably from 7 to 9. The pH can be adjusted by means of an alkali, for example ammonia, mono-, di- or tri-ethanolamine, di- or tri- sodium phosphate, or sodium or potassium carbonate, or by means of an acid, for example acetic acid, lactic acid, phosphoric acid or citric acid.

The dyeing of keratin fibers, particularly living human hair, by means of the dyeing compositions according to the present invention can be carried out in the usual way by applying the composition to the fibers to be dyed, leaving it in contact therewith for about 5 to 30 minutes, and then rinsing the fibers and optionally washing them and drying them.

Depending on the nature of the substituents, the indoanilines of the present invention make it possible to obtain a very wide range of colors ranging from greens to violets via blues; only yellows and oranges are not represented. The dyeings obtained are notable for their luminous nature and their rich sheen, especially a pearly or metallic sheen.

When the compositions according to the invention are in the form of aqueous-alcoholic solutions, they can also contain a cosmetic resin, in which case they form what are commonly called colored wavesetting lotions, which can be applied to wet hair before setting it in waves. These compositions generally contain about 0.001 to 0.5% of a compound of formula (I).

Representative cosmetic resins which can be used in such wavesetting lotions according to this invention include such film-forming polymers as polyvinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate, copolymers of vinyl acetate and an unsaturated carboxylic acid such as crotonic acid, copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and an acrylic or methacrylic ester, copolymers resulting from the copolymerization of vinyl acetate and an alkyl vinyl ether, copolymers resulting from the copolymerization of vinyl acetate, crotonic acid and a vinyl ester of an acid with a long carbon chain (i.e. more than 8 carbon atoms) or an allyl or methallyl ester of an acid with a long carbon chain, copolymers resulting from the copolymerization of an ester derived from an unsaturated alcohol and from an acid with a short carbon chain (i.e. not more than 8 carbon atoms), an unsaturated acid with a short chain and at least one ester derived from a saturated alcohol with a short chain and from an unsaturated acid, and copolymers resulting from the copolymerization of at least one unsaturated ester and at least one unsaturated acid.

Representative preferred resins include polyvinylpyrrolidone having a molecular weight of 10,000 to 360,000; copolymers comprising 10% of crotonic acid and 90% of vinyl acetate having a molecular weight of 10,000 to 70,000; copolymers of vinylpyrrolidone (VP) and vinyl acetate (VA) with a molecular weight of 30,000 to 200,000, the VP/VA ratio being from 30/70 to 70/30; copolymers of maleic anhydride and methyl vinyl ether, the specific viscosity of which, measured at 25° C as 1 g/100 ml solution in methyl ethyl ketone, is from 0.1 to 3.5 centipoises, the ethyl, isopropyl and butyl monoesters of copolymers of maleic anhydride and methyl vinyl ether; copolymers of maleic anhydride and butyl vinyl ether; terpolymers of methyl methacrylate (15-25%), stearyl methacrylate (25-35%) and dimethylaminoethyl methacrylate (52-62%), preferably quaternized, for example by means of dimethyl-sulphate, the viscosity of which, measured at the boiling point of the ether as 5% solution in dimethylformamide, is from 8 to 12 centipoises; and terpolymers of vinyl acetate (75-85%), allyl stearate (10-20%) and allyloxy-acetic acid (3-10%), the viscosity of which, measured at the boiling point of the ether as a 5% solution in dimethylformamide, is from 4.4 to 5 centipoises.

These resins are generally used in an amount from 1 to 3% by weight of the total weight of the composition.

The alcohols which are suitable for producing wavesetting lotions according to the invention are alcohols of low molecular weight, preferably ethanol or isopropanol. These alcohols are suitably employed in an amount from 20 to 70% by weight.

The wavesetting lotions according to the present invention can be employed in the usual way, by applying them to wet hair which has been washed and rinsed beforehand, constraining in a deformed state, for example by winding up on curlers and drying the hair.

The dye composition of the present invention can include a surface active agent as a carrier or as a thickening agent. Representative surface active agents that can usefully be employed include oxyethylenated alcohols, particularly oxyethylenated lauryl alcohol; partially sulfated oxyethylenated lauryl alcohol and preferably a mixture consisting of 19% lauryl alcohol oxyethylenated with 2 moles of ethylene oxide and 81% of the sodium sulfate salt of this same oxyethylenated alcohol; the alkaline or ammonium sulfate salts of long chain fatty alcohols, for example, ammonium lauryl sulfate; and oxyethylenated alkylphenols and preferably nonylphenol oxyethylenated with 4 or 9 moles of ethylene oxide per mole of alkylphenol. The surface active agent is generally employed in amounts of about 2 to 30 percent by weight of said composition.

The invention is illustrated by the following examples which are tabulated in Tables I, II, III and IV.

Examples pertaining to the preparation of the dyes of the present invention appear in Tables I and II. Table I which provides data concerning the characteristics of the prepared benzopquinoneimine dyes of this invention has columns numbered 1 through 9 inclusive. Column 1 indicates the number of the Example; Column 2 identifies the benzoquinoneimine prepared; Column 3 gives the melting point of the prepared benzoquinoneimine; Column 4 provides the empirical formula for the prepared benzoquinoneimine; and Columns 5 through 9 tabulate respectively the percentages of C, H, N, Cl and S in said dye. For each compound prepared, columns 5 through 9 carry two or three lines. The first line indicates the theoretical percentage of the indicated element corresponding to the empirical formula of column 4; line 2, and when provided, line 3 indicate the percentages found by analysis.

Table II which synopsizes the process by which the benzoquinones appearing in Table I are prepared, has eight columns numbered 1 and 10-16. Column 1 indicates, as in Table I, the number of the Example of preparation; Column 10 indicates the substituted aniline initial reactant; Column 11 identifies the substituted phenol initial reactant; Column 12 gives the molar ratio of the substituted phenol of Column 11 to the substituted aniline of Column 10; Column 13 identifies the reaction medium employed; Column 14 lists when appropriate the particular oxidizing agent used; Column 15 indicates, also when appropriate, the molar ratio of the oxidizing agent of Column 14 to phenol of Column 11; and Column 16 identifies the reaction temperature employed in degrees centigrade.

The benzoquinoneimines of Examples 1 to 8 are prepared by the reaction of a substituted nitroso aniline of the formula ##STR7## on a substituted phenol of formula (V), in ethanol or a 1:1 ethanol-water mixture made alkaline by sodium hydroxide and in the absence of an oxidizing agent.

The benzoquinoneimines of Example 9 and following are prepared by the reaction of a substituted p-phenylenediamine (substituted aniline) of the formula (VII) ##STR8## on a substituted phenol of formula (V). The molar ratio of substituted phenol : substituted aniline can be between 1:0.5 and 1:1.2 and preferably between 1:0.65 and 1:1. The molar ratio of oxidizing agent : phenol is between 1:1 and 4:1 when there is employed, as the oxidizing agent, ammonium persulfate or potassium ferricyanide. This molar ratio however is from 8:1 when there is used, as the oxidizing agent, hydrogen peroxide. The latter is generally employed in the form of a 6 weight percent solution. The reaction medium comprises water, a lower alkanol, preferably ethanol, propanol or isopropanol, an acetone-water mixture or a lower alkanol-water mixture, both generally in a 1:1 volume ratio. The pH of the reaction medium is alkalinized to a pH of at least 8, preferably by the addition thereto of an alkalizing agent such as ammonia or an alkaline carbonate.

The Examples of use include not only examples of simple dye compositions which are tabulated in Table IV, but also of dye compositions containing a cosmetic film forming resin. The latter compositions are often referred to as hair setting lotions and are tabulated in Table III.

Table III contains 12 columns numbered from 11 to 22. Column 11 indicates the number of the Example of the hair setting lotion. The column carries a number preceded by the letter M. Column 12 indicates the number of the Example of preparation according to which is prepared the benzoquinoneimine used as the dye or the letter C followed by a number which represents another dye used in admixture with the benzoquinoneimine. The name of this additional dye appears at the bottom of the table. Column 13 indicates the amount of dye expressed in weight percent of the total weight of the composition. Columns 14-17 concern the cosmetic resin used. Column 14 indicates the name of the resin and column 15 its average molecular weight. Column 16 reports the viscosity of the resin in centipoises while Column 17 indicates the weight percent of the resin relative to the total weight of the composition. Columns 18 and 19 reveal, respectively, the name and the weight percent (relative to the total weight of the composition), of the alcohol used. Column 20 indicates the pH of the composition while Column 22 indicates the color obtained on the bleached hair (D) or 95% naturally white hair (B 95). This latter indication of the type of hair to which the composition is applied appears in column 21. In Column 14, the name of the resin, polymer or copolymer, is indicated by abbreviations. These abbreviations and their meaning are as follows: PVP = polyvinylpyrrolidone; VA/CA = copolymer of vinyl acetate and crotonic acid; VP/VA = copolymer of vinylpyrrolidone and vinyl acetate; and MM/StM/DEM = copolymer of methyl methacrylate (15-25%)/stearyl methacrylate (25-35%)/dimethylaminoethyl methacrylate (52-62%) quaternized with dimethyl sulfate.

The viscosity of the VP/VA copolymer is measured at 25° C in a 5% solution in ethanol. The viscosity of the terpolymer MM/StM/DEM is measured at the boiling point of ether (35° C) and at a concentration of 5% in dimethylformamide.

Table IV carries 12 columns numbered from 31 to 42. Column 31 indicates the number of the Example of the dye composition. This column carries a number preceded by the letter T. Column 32 indicates the number of the Example of preparation according to which is prepared the benzoquinoneimine used as the dye or the letter C followed by a number which represents another dye used in admixture with the benzoquinoneimine and for which the name appears at the bottom of the Table. Columns 34 and 35 indicate respectively the nature and the weight percent of the surface active agent used. Column 33 indicates the amount of dye employed, expressed in weight percent. Columns 36 and 37 indicate, respectively, the name and weight percent of the solvent used while Columns 38 and 39 indicate the name and weight percent of the adjuvant used. Column 40 indicates the pH of the composition and Column 42 indicates the color obtained on bleached hair (D) or on 95% naturally white hair (B 95). This latter indication of the type of hair to which the composition is applied appears in Column 41. All percents indicated are by weight of the total weight of the composition.

In Columns 34 and 38, the name of the surface active agent and various adjuvants are indicated by abbreviations, the meanings of which appear at the bottom of the Table.

                                      TABLE I                                      __________________________________________________________________________     Ex.                    Melting                                                                            Empirical                                                                             C     H    N     Cl    S                     NO.                                                                               BENZOQUINONEIMINE   Point                                                                              Formula                                                                               %     %    %     %     %                     (1)                                                                                 (2)               (°C)(3)                                                                     (4)    (5)   (6)  (7)   (8)   (9)                   __________________________________________________________________________      1 N-[(4'-ethylamino)phenyl]-2-                                                                       225 C.sub.17 H.sub.20 N.sub.4 O.sub.2                                                     65.36 6.45 17.94                                methyl-5-carbamylmethylamino   65.06 6.59 18.16                                benzoquinoneimine              65.08 6.64 18.04                              2 N-[(4'-ethylamino-2'-                                                                              128 C.sub.17 H.sub.21 N.sub.3 O                                                           72.05 7.47 14.83                                methyl)phenyl]-2,6-dimethyl    72.38 7.62 15.12                                3-amino benzoquinoneimine      72.45 7.51 15.09                              3 N-[(4'-ethylamino-2'-                                                                              182 C.sub.16 H.sub.19 N.sub.3 O                                                           71.34 7.11 15.60                                methyl)phenyl]-2-methyl        71.41 7.21 15.76                                5-amino benzoquinoneimine      71.32 7.32 15.82                              4 N-[(4'-ethylamino)phenyl]-                                                                         184 C.sub.14 H.sub.14 N.sub.3 O.sub.Cl                                                    60.98 5.09 15.25 12.87                          2-chloro-5-amino               61.07 5.17 15.24 12.92                          benzoquinoneimine              60.94 5.14 15.34 13.90                        5 N-[(4'-ethylamino-3'-                                                                              147 C.sub.17 H.sub.21 N.sub.3 O                                                           72.05 7.47 14.83                                methyl)phenyl-2,6-dimethyl-    71.78 7.42 15.04                                3-amino benzoquinoneimine      71.67 7.53 14.65                              6 N-[(4'-ethylamino)phenyl]-                                                                         162 C.sub.16 H.sub.19 N.sub.3 O                                                           71.34 7.11 15.60                                2,6-dimethyl-3-amino           71.12 7.11 15.79                                benzoquinoneimine              71.28 6.90 15.76                              7 N-[(4'-methylamino-2',5'-                                                                          210 C.sub.17 H.sub.21 N.sub.3 O                                                           72.05 7.47 14.83                                dimethyl)phenyl]-2,6-dimethyl-3-                                                                              71.94 7.77 14.81                                amino benzoquinoneimine                                                      8 N-[(4'-methylamino)phenyl]-                                                                        162 C.sub.14 H.sub.15 N.sub.3 O                                                           69.69 6.27 17.42                                2-methyl-5-amino               68.52 6.33 17.62                                benzoquinoneimine              68.57 6.39 17.55                              9 N-[(4'-methylamino-3'-                                                                             156 C.sub.16 H.sub.18 N.sub.2 O.sub.2                                                     71.09 6.71 10.36                                methoxy)phenyl]-2,6-dimethyl   70.86 6.83 10.42                                benzoquinoneimine              70.79 6.76 10.49                             10 N-[(4'-methylamino)phenyl]-                                                                        166 C.sub.15 H.sub.17 N.sub.3 O                                                           70.56 6.71 16.46                                2,6-dimethyl 3-amino    MW = 255 (1)                                                                          70.75 6.67 16.49                                benzoquinoneimine       251 (2)                                                                               70.41 6.68 16.52                             11 N-[(4'-ethylamino 2'-                                                                              222 C.sub.16 H.sub.17 N.sub.4 O.sub.2 Cl                                                  57.74 5.11 16.87 10.67                          methyl)phenyl] 3-chloro        57.26 5.04 16.61 10.41                          6-ureido benzoquinoneimine     57.30 5.21 16.71 10.47                       12 N-[(4'-butylamino 3'-                                                                               87 C.sub.19 H.sub.22 N.sub.3 O.sub.2 Cl                                                  63.42 6.16 11.67 9.85                           chloro)phenyl]-2-methyl        63.06 6.16 11.87 9.69                           5-acetylamino benzoquinoneimine                                                                               63.14 6.23 11.73 9.66                        13 N-[(4'-ethylamino 2'-                                                                              212 C.sub.16 H.sub.18 N.sub.4 O.sub.2                                                     64.41 6.08 18.78                                methyl)phenyl]-3-ureido        64.29 6.25 18.62                                benzoquinoneimine              64.58 6.09 18.62                             14 N-[(4'-methylamino)phenyl]-                                                                        158 C.sub.17 H.sub.19 N.sub.3 O.sub.2                                                     68.66 6.44 14.13                                2,6-dimethyl 3-acetylamino     68.29 6.57 14.25                                benzoquinonemine               68.32 6.58 14.34                             15 N-[(4'-ethylamino 2' -                                                                             162 C.sub.17 H.sub.18 N.sub.3 O.sub.2 Cl                                                  61.54 5.43 12.67 10.71                          methyl)phenyl]-3-chloro        60.98 5.26 12.97 10.39                          6-acetylamino benzoquinoneimine                                                                               61.22 5.25 12.86 10.45                       16 N-[(4'-ethylamino)phenyl]-                                                                         100 C.sub.17 H.sub.19 N.sub. 3 O.sub.2                                                    68.66 6.44 14.13                                2-methyl-5-acetyl-amino        68.12 6.44 13.98                                benzoquinoneimine              68.41 8.66 13.94                             17 N-[(4'-butylamino-3'-                                                                              124 C.sub.18 H.sub.20 N.sub.3 O.sub.2 Cl                                                  62.52 5.80 12.15 10.25                          chloro)phenyl] 3-acetylamino   62.35 6.03 12.21 10.40                          benzoquinoneimine              62.29 6.04 12.09 10.17                       18 N-[(4'-ethylamino)phenyl]-                                                                         198 C.sub.16 H.sub.16 N.sub.3 O.sub.2 Cl                                                  60.47 5.04 13.22                                2-chloro 5-acetyl-amino        59.98 4.97     13.21                            benzoquinoneimine              59.85 5.06 13.17                             19 N-[(4'-ethylamino-3'chloro)phenyl]                                                                 144 C.sub.17 H.sub.18 N.sub.3 O.sub.2 Cl                                                  61.53 5.46 12.66 10.68                          2-methyl 5-acetylamino         61.57 5.61 12.53 10.79                          benzoquinoneimine              61.28 5.51 12.86 10.65                       20 N-[(4'-(β-acetylamino-                                                                        126 C.sub.17 H.sub.18 N.sub.3 O.sub.2 Cl                                                  61.54 5.46 12.64 10.70                          ethyl)amino phenyl]3-methyl    61.24 5.60 12.55 10.59                          6-chloro benzoquinoneimine     61.32 5.54 12.47 10.48                       21 N-[(4'-(β-hydroxyethyl)amino phenyl]                                                          206 C.sub.14 H.sub.14 N.sub.3 O.sub.2 Br                                                  50.00 4.16 12.50 23.84                          2-bromo-5-amino benzoquinoneimine                                                                             50.12 4.35 12.60 23.62                                                         50.24 4.28 12.36 23.65                       22 N-[(4'-β-hydroxyethylamino-3'-                                                                242 C.sub.18 H.sub.21 N.sub.3 O.sub.3                                                     66.03 6.47 12.84                                methyl)phenyl] 2-methyl-5-     65.85 6.65 12.93                                acetylamino benzoquinoneimine  65.87 6.44 13.06                             23 N-[(4'-β-morpholinoethylamino)                                                                180 C.sub.20 H.sub.23 N.sub.4 O.sub.3 Cl                                                  59.62 5.71 13.91 8.81                           phenyl]-2-chloro 5-acetylamino 59.03 5.61 14.06 8.72                           benzoquinoneimine              58.98 5.87 14.18 8.74                        24 N-[(4'-β-morpholinoethylamino)                                                                178 C.sub.19 H.sub.23 N.sub.5 O.sub.                                                      61.77 6.28 18.96                                phenyl]-3-ureido               61.05 6.26 18.82                                benzoquinoneimine              61.28 6.22 18.75                             25 N-[(4'-β-mesylamino-ethylamino)                                                               126 C.sub.18 H.sub.22 N.sub.4 O.sub.4 S                                                   55.38 5.68 14.35                                phenyl]-2-methyl 5-acetylamino 55.02 5.97 14.35                                benzoquinoneimine              55.17 5.82 14.43                             26 N-[(4'-β-acetylaminoethylamino)                                                               230 C.sub.17 H.sub.18 N.sub.5 O.sub.3 Cl                                                  54.33 4.80 18.64                                phenyl]-3-chloro-6-ureido      54.22 5.11 18.67                                benzoquinoneimine              54.48 5.08 18.55                             27 N-[(4'-β-hydroxyethylamino-3'-                                                                150 C.sub.16 H.sub.19 N.sub.3 O.sub.3                                                     63.77 6.36 13.95                                methoxy)phenyl] 2-methyl-5-amino                                                                              63.81 6.53 14.02                                benzoquinoneimine              64.02 6.65 14.19                             28 N-[(4'-β-mesylaminoethylamino-3'-                                                             148 C.sub.20 H.sub.26 N.sub.4 O.sub.4 S                                                   57.40 6.26 13.39       7.64                     methyl)phenyl]-2,6-dimethyl-5- 57.52 6.24 13.53       7.66                     acetylamino benzoquinoneimine  57.23 6.27 13.45       7.44                  29 N-[(4'-β-acetylaminoethylamino-                                                               183 C.sub.19 H.sub.24 N.sub.4 O.sub.3                                                     64.02 6.79 15.72                                3'-methoxy)phenyl]-2,6-dimethyl-5-                                                                            63.87 6.58 15.51                                amino benzoquinoneimine        63.74 6.70 15.20                             30 N-[(4'-β-mesylamino ethylamino-                                                               244 C.sub.18 H.sub.21 N.sub.4 O.sub.4 S                                                   50.88 4.98 13.18       7.54                     3'-chloro)phenyl]-2-methyl-5-  50.71 5.20 13.36       7.26                     acetylamino benzoquinoneimine  50.77 5.20 13.42       7.38                  31 N-[(4'-β-acetylamino-3'-                                                                      161 C.sub.18 H.sub.20 N.sub.3 O.sub.2                                                     62.51 5.79 12.15 10.27                          chloro)phenyl]-2,6-dimethyl    62.29 5.80 12.21 10.23                          benzoquinoneimine              62.36 5.94 12.10 10.38                       32 N-[(4'-β-hydroxyethylamino-                                                                   165 C.sub.17 H.sub.21 O.sub.3 N.sub.3                                                     64.74 6.71 13.33                                3'-methoxy)phenyl]-2,6-dimethyl-                                                                              64.66 6.78 13.17                                5-amino benzoquinoneimine      64.50 6.78 13.15                             33 N-[(4'-βhydroxyethylamino-                                                                    110 C.sub.19 H.sub.23 O.sub.4 N.sub.3                                                     60.79 6.71 11.19                                3'-methoxy)phenyl]2,6-dimethyl-                                                                        . H.sub.2 O                                                                           60.53 6.58 11.31                                5-acetylamino benzoquinoneimine                                                                               60.45 6.61 11.36                             34 N-[(4'-β-hydroxyethylamino-                                                                   144 C.sub.16 H.sub.15 N.sub.3 O.sub.3 Cl.sub.2                                            52.19 4.10 11.41 19.26                          3'-chloro)phenyl]-3-chloro 6-  52.05 4.42 11.52 19.16                          acetylamino benzoquinoneimine  51.93 4.38 11.36 19.23                       35 N-[ (4'-β-aminoethylamino-                                                                    168 C.sub.18 H.sub.24 N.sub.4 O.sub.2                                                     65.83 7.37 17.06                                3'-methyl-6'-methoxy)phenyl]-2,6-                                                                             65.12 7.03 16.98                                dimethyl-3-amino benzoquinoneimine                                                                            65.24 7.17 16.84                             36 N-[(4'-β-mesylaminoethylamino-                                                                242 C.sub.19 H.sub.24 N.sub.4 O.sub.4 S                                                   56.43 5.98 13.86       7.91                     3'-methyl)phenyl]-2-methyl-5-  56.41 6.04 14.07       7.74                     acetylamino benzoquinoneimine  56.58 6.21 14.12       7.84                  37 N-[(4'β-acetylaminoethylamino-                                                                222 C.sub.18 H.sub.21 N.sub.5 O.sub.3                                                     60.83 5.96 19.71                                3'-methyl)phenyl]-             60.66 6.16 19.61                                3-ureido benzoquinoneimine     60.57 5.97 19.70                             38 N-[(4'-β-carbamylmethylamino-                                                                 240 C.sub.19 H.sub.22 N.sub.4 O.sub.3                                                     64.39 6.26 15.81                                3'-methyl)phenyl]-2,6-dimethyl-                                                                               64.98 6.47 15.45                                3-acetylamino benzoquinoneimine                                                                               64.87 6.53 15.78                             39 N-[(4'-γ-morpholinopropylamino-                                                              214 C.sub.21 H.sub.24 N.sub.4 O.sub.3 Cl.sub.2                                            55.87 5.36 12.41 15.74                          3'-chloro)phenyl]-3-chloro-6-                                                                          MW 451 (1)                                                                            55.58 5.56 12.56 15.78                          acetylamino benzoquinoneimine                                                                          448 (2)                                             40 N-[(4'-methylamino)phenyl]-                                                                        132 C.sub.15 H.sub.16 N.sub.2 O                                                           74.97 6.71 11.66                                2,6-dimethyl benzoquinoneimine 4.68  6.91 11.44                                                        MW 240 (1)                                                                     239 (2)                                             41 N-[(4'-methylamino-3'-methyl)                                                                      160 C.sub.18 H.sub.21 N.sub.3 O.sub.2                                                     69.43 6.80 13.50                                phenyl]-2,6-dimethyl-3-        69.36 6.73 13.28                                acetylamino benzoquinoneimine                                               42 N-[(4'-methylamino-2'-methyl)                                                                      218 C.sub.18 H.sub.21 N.sub.3 O.sub.2                                                     69.43 6.80 13.50                                phenyl]-2,6-dimethyl 3-        69.60 6.68 13.27                                acetylamino benzoquinoneimine                                               43 N-[(4'-methylamino-2'-methyl)                                                                      138 C.sub.16 H.sub.18 N.sub.2 O                                                           75.56 7.13 11.02                                phenyl]-2,6-dimethyl           75.69 7.12 11.11                                benzoquinoneimine                                                           44 N-[(4'-methylamino-2-'-                                                                             129.5                                                                             C.sub.16 H.sub.18 N.sub.2 O                                                           75.56 7.13 11.02                                methyl)phenyl]-2,6-dimethyl    75.61 7.01 11.32                                benzoquinoneimine       MW 254 (1)                                                                     260 (2)                                             45 N-[(4'-β-hydroxyethylamino-                                                                   163 C.sub.18 H.sub.21 N.sub.3 O.sub.4                                                     62.96 6.16 12.24                                2'-methoxy)phenyl]-2-methyl-   62.76 6.31 12.24                                5-acetylamino benzoquinoneimine                                             46 N-[(4'-β-acetylaminoethylamino-                                                               156 C.sub.17 H.sub.18 N.sub.3 O.sub.3 Cl                                                  58.70 5.18 12.08                                3'-chloro)phenyl]-3-           58.41 4.97 12.20                                methoxy benzoquinoneimine      58.56 5.04 12.17                             47 N-[(4'-βmesylaminoethylamino)                                                                 157 C.sub.19 H.sub.24 N.sub.4 O.sub.4 S                                                   56.43 5.98 13.86       8.07                     phenyl]-2,6-dimethyl-3-        56.30 6.00 13.98       7.91                     acetylamino benzoquinoneimine                                               48 N-[(4'-β-hydroxyethylamino)                                                                   162 C.sub.17 H.sub.19 N.sub.3 O.sub.3                                                     65.16 6.11 13.41                                phenyl[-2-methyl 5-acetylamino 65.16 6.25 13.63                                benzoquinoneimine                                                           49 N-[(4'-β-hydroxyethylamino-                                                                   166 C.sub.17 H.sub.20 N.sub.2 O.sub.3                                                     67.98 6.71 9.33                                 3'-methoxy)phenyl]-2,6-dimethyl                                                                               67.90 6.72 9.30                                 benzoquinoneimine                                                           __________________________________________________________________________      (1) Molecular weight calculated                                                (2) Molecular weight determined by potentiometric titration in acetic aci      using perchloric acid                                                         ANALYSIS                                                                       Ex.                    Melting                                                                              Empirical  C     H    N     Cl                    No.                                                                               BENZOQUINONEIMINE   Point Formula    %     %    %     %                     (1)                                                                                 (2)               (°C)(3)                                                                       (4)        (5)   (6)  (7)   (8)                   __________________________________________________________________________     50 N-[(4'-γ-morpholinopropylamino-                                                              212   C.sub.19 H.sub.22 N.sub.4 Br.sub.2 ClO.sub.2                                              50.17 4.85 12.35                          3'-chloro)phenyl]-2-bromo-5-         50.10 5.06 12.65                          amino benzoquinoneimine                                                     51 N-[(4'-methylamino-2'-methoxy)                                                                     249   C.sub.18 H.sub.21 N.sub.3 O.sub.3                                                         66.03 6.47 12.84                          phenyl]-2,6-dimethyl-5-              65.84 6.52 12.79                          acetylamino benzoquinoneimine                                               52 N-[(4'-methylamino-2'-methoxy)                                                                     204   C.sub.17 H.sub.19 N.sub.3 O.sub.3                                                         65.16 6.11 13.41                          phenyl]-2-methyl-5-acetylamino       64.92 6.19 13.34                          benzoquinoneimine                                                           53 N-[(4'-methylamino 3'-methoxy)                                                                     195   C.sub.16 H.sub.19 N.sub.3 O.sub.2                                                         67.34 6.71 14.73                          phenyl]-2,6-dimethyl-5-amino         67.20 6.71 14.99                          benzoquinoneimine                                                           54 N-[(4'-methylamino 2'-methoxy)                                                                     178   C.sub.16 H.sub.17 N.sub.3 O.sub.2.                                             0.5H.sub.2 O                                                                              64.28 6.42 15.00                          phenyl]-2-methyl-5-amino             64.26 6.61 14.87                          benzoquinoneimine                                                           55 N-[(4'-methylamino-3'-chloro)                                                                      206   C.sub.16 H.sub.16 Cl N.sub.3 O.sub.2                                                      60.45 5.07 13.22                          phenyl]-2-methyl-5-acetylamino       60.35 5.23 13.31                          benzoquinoneimine                                                           56 N-[-(4'-methylamino-3'-chloro)                                                                     166   C.sub.17 H.sub.18 Cl N.sub.3 O.sub.2                                                      61.53 5.47 12.66 10.68                    phenyl]-2,6-dimethyl-5-acetylamino   61.61 5.62 12.51 10.53                    benzoquinoneimine                                                           57 N-[(4'-methylamino-3'-chloro)                                                                      127   C.sub.15 H.sub.15 Cl N.sub.2 O                                                            65.58 5.50 10.19 12.90                    phenyl]-2,6-dimethyl                 65.41 5.60 10.24 12.90                    benzoquinoneimine                                                           58 N-[(4'-methylamino-3'-chloro)                                                                      165   C.sub.5 H.sub. 16 Cl N.sub.3 O                                                            60.30 5.70 14.01 11.91                    phenyl]-2,6-dimethyl-5-amino                                                                             .0.5H.sub.2 O                                                                             60.64 5.70 14.07 11.98                    benzoquinoneimine                                                           59 N-[(4'-methylamino-3'-chloro)                                                                      174   C.sub.14 H.sub.14 Cl N.sub.3 O                                                            60.98 5.11 15.24 12.86                    phenyl]-2-methyl-5-amino             61.17 5.32 15.10 12.67                    benzoquinoneimine                                                           60 N-[(4'-methylamino-2'-chloro)                                                                      235   C.sub.17 H.sub.18 Cl N.sub.3 O.sub.2                                                      61.53 5.47 12.66 10.68                    phenyl] -2,6-dimethyl-5-acetylamino  61.26 5.56 12.90 10.47                    benzoquinoneimine                                                           61 N-[(4'-methylamino-2'-chloro)                                                                      182   C.sub.15 H.sub.16 N.sub.3 OCl                                                             62.16 5.56 14.50 12.23                    phenyl]-2,6-dimethyl-5-amino         61.92 5.71 14.30 12.05                    benzoquinoneimine                                                           62 N-[(4'-methylamino-2'chloro)                                                                       180   C.sub.14 H.sub.14 N.sub.3 O                                                               60.98 5.11 15.24 12.86                    phenyl]-2-methyl-5-amino             60.83 4.99 15.10 12.74                    benzoquinoneimine                                                           63 N-[(4'-methylamino-2'-chloro)                                                                      234   C.sub.16 H.sub.16 N.sub.3 O.sub.2 Cl                                                      60.47 5.07 13.22                          phenyl]-2-methyl-5-acetylamino       60.42 5.29 13.18                          benzoquinoneimine                                                           64 N-[(4'-methylamino-3'-methoxy)                                                                     120   C.sub.18 H.sub.21 N.sub.3 O.0.5H.sub.2                                                    64.28 6.54 12.50                          phenyl]-2,6-dimethyl-5-acetylamino                                                                  158(1)          64.52 6.78 12.69                          benzoquinoneimine                                                           65 N-[(4'-methylamino-2'-chloro)                                                                      190   C.sub.16 H.sub.18 N.sub.3 O.sub.2 Cl                                                      60.09 5.67 13.14 11.11                    phenyl]-2-methyl-5-β            60.15 5.86 13.31 11.19                    hydroxyethylamino benzoquinoneimine                                         66 N-[(4'-methylamino-2'-methoxy)                                                                     152   C.sub.16 H.sub.18 N.sub.2 O.sub.2                                                         71.09 6.71 10.36                          phenyl]-2,6-dimethyl                 71.40 6.91 10.15                          benzoquinoneimine                                                           67 N-[(4'-methylamino-2'-methoxy)                                                                     200   C.sub.16 H.sub.19 N.sub.3 O.sub.2                                                         67.34 6.71 14.73                          phenyl]-2,6-dimethyl-5-amino         67.25 6.57 14.77                          benzoquinoneimine                                                           68 N-[(4'-methylamino-2'-methyl)                                                                      140   C.sub.15 H.sub.17 N.sub.3 O.O.5H.sub.2                                                    68.16 6.86 15.90                          phenyl]2-methyl-5-amino              68.35 6.99 16.11                          benzoquinoneimine                                                           69 N-[(4'-methylamino-2'-methyl)                                                                      149   C.sub.16 H.sub.19 N.sub.3 O                                                               71.34 7.11 15.60                          phenyl]-2,6-dimethyl-5-amino         71.30 7.03 15.59                          benzoquinoneimine                                                           70 N-[(4'-methylamino-2'-chloro)                                                                      138   C.sub.15 H.sub.15 N.sub.2 O                                                               65.57 5.50 10.20 12.91                    phenyl]-2,6-dimethyl                 65.56 5.74 10.35 12.76                    benzoquinoneimine                                                           71 N-[(4'-methylamino-2'-methyl)                                                                      175   C.sub.17 H.sub.19 N.sub.3 O.sub.2                                                         68.66 6.44 14.13                          phenyl]-2-methyl-5-acetylamino       68.66 6.63 14.35                          benzoquinoneimine                                                           72 N-[(4'-methylamino-3'-methyl)                                                                      152   C.sub.16 H.sub.19 N.sub.3 O                                                               71.34 7.11 15.60                          phenyl]-2,6-dimethyl-5-amino         71.20 7.01 15.73                          benzoquinoneimine                                                           73 N-[(4'-methylamino-3'-methyl)                                                                      210   C.sub.17 H.sub.19 N.sub.3 O                                                               68.66 6.44 14.13                          phenyl]-2-methyl-5-acetylamino       68.64 6.49 14.28                          benzoquinoneimine                                                           74 N-[(4' -methylamino-3'-methyl)                                                                     166   C.sub.15 H.sub.17 N.sub.3 O                                                               70.56 6.71 16.46                          phenyl]-2-methyl-5-amino             70.33 6.72 16.34                          benzoquinoneimine                                                           75 N-[(4'-methylamino)phenyl]-                                                                        161   C.sub.16 H.sub.17 N.sub.3 O.sub.2                                                         67.82 6.05 14.83                          2-methyl-5-acetylamino               67.72 6.18 14.92                          benzoquinoneimine                                                           76 N-[(4'methylamino-3'-methoxy)                                                                      179   C.sub.18 H.sub.21 N.sub.3 O.sub.4                                                         62.96 6.16 12.24                          phenyl]-2-methyl-5-                  63.02 6.28 12.06                          carbethoxyamino benzoquinoneimine                                           77 N-[(4'-methylamino-3'-chloro)                                                                      228   C.sub.15 H.sub.15 N.sub.4 O.sub.2 Cl                                                      56.51 4.71 17.58 11.14                    phenyl]-2-methyl-5-ureido            56.61 4.90 17.63 10.93                    benzoquinoneimine                                                           78 N-[(4'-β-hydroxyethylamino-3'-                                                                195   C.sub.17 H.sub.19 N.sub.4 O.sub.3 Cl                                                      56.30 5.24 15.42 9.79                     chloro)phenyl]-2,6-dimethyl-3-       56.41 5.34 15.33 9.81                     ureido benzoquinoneimine                                                    79 N-[(4'-β-hydroxyethylamino-3'-                                                                280   C.sub.15 H.sub.15 N.sub.4 O.sub.3 Cl                                                      53.81 4.48 16.74 10.61                    chloro)phenyl]-3-ureido              53.86 4.71 16.62 10.36                    benzoquinoneimine                                                           80 N-[(4'-β-hydroxyethylamino-3'-                                                                178   C.sub.16 H.sub.16 N.sub.3 O.sub.3 Cl                                                      57.57 4.79 12.59 10.64                    chloro)phenyl]-3-acetylamino         57.39 4.79 12.71 10.48                    benzoquinoneimine                                                           81 N-[(4'-β-hydroxyethylamino-3'-                                                                176   C.sub.17 H.sub.18 N.sub.3 O.sub.3 Cl                                                      58.70 5.18 12.08 10.21                    chloro)phenyl]-2-methyl-5-           58.83 5.19 12.17 10.36                    acetylamino benzoquinoneimine                                               82 N-[(4'-β-hydroxyethylamino-3'-                                                                240   C.sub.16 H.sub.17 N.sub.4 O.sub.3 Cl                                                      55.09 4.88 16.07 10.18                    chloro)pheny l]-2-methyl-5-ureido    54.84 4.97 16.03 10.18                    benzoquinoneimine                    54.83 4.91 16.00 10.30                 __________________________________________________________________________      (1) Double melting point                                                      Ex.                    Melting                                                                              Empirical  C     H    N   Cl S                    NO.                                                                               BENZOQUINONEIMINE   Point Formula    %     %    %   %  %                    (1)                                                                                 (2)               (° C)(3)                                                                      (4)        (5)   (6)  (7) (8)                                                                               (9)                  __________________________________________________________________________     83 N-[(4'-methylamino)phenyl]-2-                                                                      228   C.sub.16 H.sub.18 N.sub.4 O.sub.2 -H.sub. 2                                    O                     17.71                          methyl-5-carbamylmethylamino                                                   benzoquinoneimine         MW 298 (1)            17.40                                                    304 (2)                                           84 N-[(4'-methylamino-2'-methyl)                                                                      200   C.sub.17 H.sub.20 N.sub.4 O.sub.2                                                                    17.94                          phenyl]-2-methyl-5-                             17.58                                                    MW 312 (1)                                           carbamylmethylamino benzoquinoneimine                                                                    315 (2)               17.68                       85 N-[(4'-methylamino-3'-methyl)                                                                      240   C.sub.17 H.sub.20 N.sub.4 O.sub.2                                                         65.36 6.45 17.94                          phenyl]-2-methyl-5-                  65.18 6.60 18.10                          carbamylmethylamino benzoquinoneimine                                       86 N-[(4'-β-acetylaminoethylamino-                                                               230 with                                                                             C.sub.19 H.sub.22 N.sub.5 O.sub.3 Cl                                                      56.50 5.45 17.35                                              decompositi-     56.20 5.53 17.45                          3'-chloro)phenyl]-2-methyl-5-                                                                      tion                                                       carbamylmethylamino benzoquinoneimine                                       87 N-[(4'-β-mesylaminoethylamine-                                                                203 with                                                                             C.sub.18 H.sub.22 N.sub.5 O.sub.4 SCl                                                     47.21 5.28 15.30                                                                              7.74                                                                              6.99                    3'-chloro)phenyl]-2-methyl-5-                                                                      decomposi-                                                                           .H.sub.2   47.34 5.15 14.98                                                                              7.78                                                                              7.03                    carbamylmethylamino benzoquinoneimine                                                              tion                        7.70                                                                               7.20                    88 N-[(4'-β-hydroxyethylamino)phenyl]                                                            235 with                                                                             C.sub.17 H.sub.20 N.sub.4 O.sub.3                                                         58.94 6.40 16.18                          2-methyl-5-carbamylmethylamino                                                                     decomposi-                                                                           .H.sub.2 O 59.15 6.26 16.33                          benzoquinoneimine   tion                                                    89 N-[(4'-β-mesylaminoethylamino-                                                                215 with                                                                             C.sub.19 H.sub.25 N.sub.5 O.sub.4 S                                                       54.40 6.01 16.70                       2-methyl-5-l)phenyl]                                                              decomposi-                54.26      5.90     16.57                            carbamylmethylamino benzoquinoneimine                                                              tion                                                    90 N-[ (4'-methylamino-3'-chloro)phenyl]                                                              120   C.sub.16 H.sub.17 N.sub.4 O.sub.2 Cl                                                      54.78 5.46                                                                               16.26                                                                               10.11                      2-methyl-5-carbamylmethylamino                                                                       212(3)                                                                             .H.sub.2 O 54.67 5.16                                                                               16.53                                                                               10.13                      benzoquinoneimine                                                           91 N-[(4'-β-mesylaminoethylamino-                                                                228   C.sub.17 H.sub.20 N.sub.5 O.sub.4 SCl                                                     47.94 4.70                                                                               16.45                                                                               8.34                                                                              7.50                    3'-chloro)phenyl]-2-methyl-5-        47.78 4.74                                                                               16.63                                                                               8.54                                                                              7.52                    ureido benzoquinoneimine                            8.47                                                                              7.56                 92 N-[(4'-β-mesylaminoethylamino-                                                                253   C.sub.16 H.sub.18 N.sub.5 O.sub.4 S                                                                      8.62                                                                              7.72                    3'-chloro)phenyl]-3-ureido                          8.70                                                                              7.94                    benzoquinoneimine                                   8.79                    93 N-[(4'-methylamino-3'-chloro)                                                                      198   C.sub. 15 H.sub.14 N.sub.3 O.sub.2 Cl                                                     59.31 4.61                                                                               13.84                           phenyl]-3-acetylamino                59.21 4.81                                                                               13.93                           benzoquinoneimine                                                           94 N-[(4'-ethylamamino-3'-methyl)                                                                     185   C.sub.18 H.sub.21 N.sub.3 O.sub.2                                                         69.45 6.75                                                                               13.50                           phenyl]-2-methyl-5-acetylamino       69.20 7.00                                                                               13.74                           benzoquinoneimine                                                           95 N-[(4'-β-hydroxyethylamino-                                                                    98   C.sub.18 H.sub.20 N.sub.3 O.sub.3 Cl                                                      59.75 5.53                                                                               11.61                           3'-chloro)phenyl]-2,6-dimethyl-3-    59.44 5.77                                                                               11.61                           acetylamino benzoquinoneimine                                               96 N-[(4'-methylamino-3'-chloro)                                                                      218   C.sub.16 H.sub.17 N.sub.4 O.sub.2 Cl                                                      57.74 5.11                                                                               16.84                           phenyl]-2,6-dimethyl-3-              57.77 5.45                                                                               16.90                           ureido benzoquinoneimine                                                    97 N-[(4'-β-hydroxyethylamino-                                                                   170   C.sub.17 H.sub.19 N.sub.4 O.sub.3 Cl                                                      53.63 5.51                                                                               14.71                           3'-chloro)phenyl]-2-methyl-5-                                                                            .H.sub.2 O 53.65 5.38                                                                               14.94                           carbamylmethylamino benzoquinoneimine                                       98 N-[(4'-mesylaminoethylamino-                                                                       230   C.sub.17 H.sub.19 N.sub.4 O.sub.4 S                                                       49.69 4.63                                                                               13.64   7.80                    3'-chloro)phenyl]-3-acetylamino      49.95 4.82                                                                               13.54   7.76                    benzoquinoneimine                                                           99 N-[(4'-methylamino-3'-chloro)                                                                      258   C.sub.14 H.sub.13 N.sub.4 O.sub.2 Cl                                                      55.17 4.27                                                                               18.39                                                                               11.66                      phenyl]-3-ureido                     55.14 4.56                                                                               18.64                                                                               11.57                      benzoquinoneimine                                                           __________________________________________________________________________      (1) molecular weight calculated                                                (2) molecular weight determined by potentiometric titration in acetic aci      using perchloric acid                                                          (3) double melting point                                                 

                                      TABLE II                                     __________________________________________________________________________                                     Molar                                                                               Reaction       Molar Reaction             Ex.                             Ratio                                                                               Medium Oxidizing                                                                              Ratio Temp.                NO.                                                                               ANILINE (Substituted) PHENOL (11):(10)                                                                           (13)   Agent   (14):(11)                                                                            (C°)          (1)                                                                                 (10)                (11)   (12) 1:1 vol ratio                                                                         (14)    (15)  (16)                 __________________________________________________________________________      1 4-nitroso-N-ethylaniline hydrochloride                                                               2-methyl-5-                                                                           1:1  Ethanol-water        50°                                    carbamyl-                                                                      methylamino                                                                    phenol                                                 2 3-methyl-4-nitroso-N-ethylaniline                                                                    2,6-dimeth-                                                                           1:1  "                    45°                                    yl-3-amino                                                                     phenol hy-                                                                     drochloride                                            3   "                   2-methyl-5-                                                                           1:1  "                    50°                                    amino phenol                                           4 4-nitroso-N-ethylaniline hydrochloride                                                               2-chloro-5-                                                                           1:1  "                    40°                                    amino phenol                                           5 2-methyl-4-nitroso-N-ethylaniline                                                                    2,6-dimeth-                                                                           1:1  "                    40°                                    yl-3-amino                                                                     phenol hy-                                                                     drochloride                                            6 4-nitroso N-ethylaniline hydrochloride                                                                 "    1:1  "                    40°            7 2,5-dimethyl-4-nitroso-N-methylaniline                                                                 "    1:1  "                    50-60°           hydrochloride                                                                8 4-nitroso-N-methylaniline                                                                            2-methyl-5-                                                                           1:1  "                    45°                                    amino phenol                                           9 2-methoxy-4-amino-N-methylaniline sulfate                                                            2,6-dimeth-                                                                           1:1  Acetone-water                                                                         Ammonium per-                                                                          2:1   0                                             yl phenol          sulfate                            10 N-methyl paraphenylenediamine dihydro-                                                               2,6-dimeth-                                                                           1:1  "      "       1:1   0                       chloride              yl-3-amino                                                                     phenol hy-                                                                     drochloride                                           11 3-methyl-4-amino-N-ethylaniline dihydro-                                                             3-chloro-6-                                                                           1:1  Isopropanol-                                                                          Ammonium                                                                               1:1   0                       chloride              ureido      water  persulfate                                                  phenol                                                12 2-chloro-4-amino-N-butylaniline sulfate                                                              2-methyl-5-                                                                           1:1  acetone-water                                                                         "       1:1   3                                             acetylamimo                                                                    phenol                                                13 3-methyl-4-amino-N-ethylaniline dihydro-                                                             3-ureido                                                                              1:1  "      "       1:1   0                       chloride              phenol                                                14 N-methyl paraphenylenediamine dihydro-                                                               2,6-dimeth-                                                                           1:1  "      "       1:1   0                       chloride              yl 3-ace-                                                                      tylamino                                                                       phenol                                                15 3-methyl-4-amino-N-ethylaniline dihydro-                                                             3-chloro-6-                                                                           1:1  "      "       2:1   0                       chloride              acetylamino                                                                    phenol                                                16 N-ethyl paraphenylenediamine dihydro-                                                                2-methyl-5-                                                                           1:1  "      "       1:1   0                       chloride              acetylamino                                                                    phenol                                                17 2-chloro-4-amino-N-butylaniline sulfate                                                              3-acetyl-                                                                             1:1  "      "       1:1   0                                             amino phenol                                          18 N-ethyl paraphenylenediamine dihydro-                                                                2-chloro-5-                                                                           1:1  water  "       2:1   0                       chloride              acetylamino                                                                    phenol                                                19 2-chloro-4-amino-N-ethylaniline sulfate                                                              2-methyl-5-                                                                           1:1  acetone-water                                                                         "       1:1   0                                             acetylamino                                                                    phenol                                                20 4-amino-N-(β-acetylamino) ethylaniline                                                          3-methyl-6-                                                                           1:1  Isopropanol-                                                                          "       2:1   0                       sulfate               chloro phenol                                                                              water                                     21 4-amino-N-(β-hydroxyethyl) aniline                                                              2-bromo-5-                                                                            1:1  Isopropanol-                                                                          Ammonium                                                                               2:1   0                       sulfate               amino phenol                                                                               water  persulfate                         22 2-methyl-4-amino-N-(β-hydroxyethyl)                                                             2-methyl-5-                                                                           1:1  Acetone-water                                                                         "       2:1   0                       aniline sulfate       acetylamino                                                                    phenol                                                23 4-amino-N-(β-morpholinoethyl) aniline                                                           2-chloro-5-                                                                           1:1  "      "       2:1   0                                             acetylamino                                                                    phenol                                                24 4-amino-N-(β-morpholinoethyl) aniline                                                           3-ureido                                                                              2:1  Isopropanol-                                                                          Potassium                                                                              4:1   0                                             phenol      water  ferricyanide                       25 4-amino-N-(β-mesylaminoethyl) aniline                                                           2-methyl-5-                                                                           1:1  "      Ammonium                                                                               2:1   0                       sulfate               acetylamino        persulfate                                                  phenol                                                26 4-amino-N-(β-acetylaminoethyl) aniline                                                          3-chloro-6-                                                                           1:1  "      "       2:1   0                       sulfate               ureido phenol                                         27 2-methoxy-4-amino-N-(β-hydroxyethyl)                                                            2-methyl-5-                                                                           1:1  "      "       1:1   +5                      aniline sulfate       amino phenol                                          28 2-methyl-4-amino-N-(β-mesylaminoethyl)                                                          2,6-dimethyl-                                                                         1:1  Acetone-water                                                                         "       1:1   0                       aniline sulfate       5-acetylamino                                                                  phenol                                                29 2-methoxy-4-amino-N-(β-acetylaminoethyl)                                                        2,6-dimethyl                                                                          1:1  Water  "       1:1   0                       aniline sulfate       5-amino                                                                        phenol                                                                         hydrochloride                                         30 2-chloro-4-amino-N-(βmesylaminoethyl)                                                           2-methyl-5-                                                                           1:1  Acetone-water                                                                         "       2:1   0                       aniline sulfate       acetylamino                                                                    phenol                                                31 2-chloro-4-amino-N-(β-acetylaminoethyl)                                                         2,6-dimeth-                                                                           1:1  Acetone-water                                                                         Ammonium                                                                               2:1   0                       aniline sulfate       yl phenol          persulfate                         32 2-methoxy-4-amino-N-(β-hydroxyethyl)                                                            2,6-dimeth-                                                                           1:1  Water  "       2:1   0                       aniline sulfate       yl-5-amino                                                                     phenol hy-                                                                     drochloride                                           33 2-methoxy-4-amino-N-(β-hydroxyethyl)                                                            2,6-dimeth-                                                                           1:1  Acetone-water                                                                         "       1.1:1 0                       aniline sulfate       yl-5-acetyl-                                                                   amino phenol                                          34 2-chloro-4-amino-N-(β-hydroxyethyl)                                                             3-chloro-6-                                                                           1:1  "      "       1:1   0                       aniline sulfate       acetylamino                                                                    phenol                                                35 2-methyl-4-amino-5-methoxy N-(β-amino-                                                          2,6-dimeth-                                                                           1:1  Ethanol-water                                                                         "       2:1   0                       ethyl) aniline trihydrochloride                                                                      yl-3-amino                                                                     phenol hy-                                                                     drochloride                                           36 2-methyl-4-amino- N-(β-mesylaminoethyl)                                                         2-methyl-5-                                                                           1:1  Acetone-water                                                                         "       2:1   0                       aniline sulfate       acetylamino                                                                    phenol                                                37 2-methyl-4-amino-N-(acetylaminoethyl)                                                                3-ureido                                                                              1:1  "      "       2:1   0                       aniline sulfate       phenol                                                38 2-methyl-4-amino-N-(carbamylmethyl                                                                   2,6-dimethyl-                                                                         1:1  Water  "       2:1   0                       aniline hydrobromide  3-acetyl-                                                                      amino phenol                                          39 2-chloro-4-amino-N(Γ-morpholinopropyl)                                                         3-chloro-6-                                                                           1:1  Acetone-water                                                                         "       2:1   20                      aniline trihydrochloride                                                                             acetylamino                                                                    phenol                                                40 N-methyl paraphenylenediamine dihydro-                                                               2,6-dimeth-                                                                           1:1  Acetone-water                                                                         Ammonium                                                                               2:1   15                      chloride              yl phenol          persulfate                         41 2-methyl-4-amino-N-methyl aniline sulfate                                                            2,6-dimeth-                                                                           1:1  "      "       2:1   10                                            yl-3-acetyl-                                                                   amino phenol                                          42 3-methyl-4-amino N-methylaniline dihydro-                                                            2,6-dimeth-                                                                           1:1  Isopropanol-                                                                          "       1:1   5                       chloride              yl-5-acetyl-                                                                               water                                                              amino phenol                                          43 2-methyl-4-amino-N-methylaniline sulfate                                                             2,6-dimethyl                                                                          1:1  acetone-water                                                                         "       2:1   15                                            phenol                                                44 Monohydrate of 3-methyl-4-amino                                                                      2,6-dimethyl                                                                          1:1  "      "       2:1   5                    N-methylaniline dihydrochloride                                                   phenol                                                                      45 3-methoxy-4-amino-N-(β-hydroxyethyl)                                                            2-methyl-5-                                                                           1:1  "      "       2:1   15                      aniline sulfate       acetylamino                                                                    phenol                                                46 2-chloro-4-amino-N-(β-acetylaminoethyl)                                                         3-methoxy                                                                             1:1  "      "       2:1   0                       aniline sulfate       phenol                                                47 N-(β-mesylaminoethyl)paraphenylenediamine                                                       2,6-dimeth-                                                                           1:1  "      "       1:1   5                       sulfate               yl-3-acetyl-                                                                   amino phenol                                          48 N-(β-hydroxyethyl)paraphenylenediamine                                                          2-methyl-5-                                                                           1:1  "      "       2:1   5                       sulfate               acetylamino                                                                    phenol                                                49 2-methoxy-4-amino N-(β-hydroxyethyl)                                                            2,6-dimethyl                                                                          1:1  Isopropanol-                                                                          "       2:1   10                      aniline sulfate       phenol      water                                     50 2-chloro-4-amino-N-(γ-morpholino propyl)                                                       2-bromo-5-                                                                            1:1  Acetone-water                                                                         Ammonium                                                                               2:1   20                      aniline trihydrochloride                                                                             amino phenol       persulfate                         51 3-methoxy-4-amino N-methylaniline dihy-                                                              2,6-dimeth-                                                                           1:0.85                                                                              "      "       2:1   0                       drochloride           yl-5-acetyl-                                                                   amino phenol                                          52 3-methoxy-4-amino-N-methylaniline dihy-                                                              2-methyl-5-                                                                           1:0.85                                                                              Isopropanol-                                                                          Potassium                                                                              2:1   0                       drochloride           acetylamino water  ferricyanide                                                phenol                                                53 Dihydrate of 2-methoxy-4-amino-N-methyl-                                                             2,6-dimeth-                                                                           1:1  Water  Ammonium                                                                               2:1   0                       aniline sulfate       yl-5-amino         persulfate                                                  phenol                                                54 3-methoxy-4-amino-N-methylaniline dihy-                                                              2-methyl-5-                                                                           1:0.85                                                                              Water- Potassium                                                                              2:1   0                       drochloride           amino phenol                                                                               isopropanol                                                                           ferricyanide                       55 2-chloro-4-amino-N-methylaniline sulfate                                                             2-methyl-5-                                                                           1:1  Acetone-water                                                                         Ammonium                                                                               2:1   1:                                            acetylamino        persulfate                                                  phenol                                                56 2-chloro-4-amino-N-methylaniline sulfate                                                             2,6-dimeth-                                                                           1:1  "      "       2:1   5                                             yl-5-acetyl-                                                                   amino phenol                                          57 2-chloro-4-amino-N-methylaniline sulfate                                                             2,6-dimethyl                                                                          1:1  "      "       2:1   10                                            phenol                                                58 2-chloro-4-amino-N-methylaniline sulfate                                                             2,6-dimeth-                                                                           1:1.10                                                                              "      H.sub.2 O.sub.2                                                                        8:1   20                                            yl-5-amino                                                                     phenol hydro-                                                                  chloride                                              59 2-chloro-4-amino-N-methylaniline sulfate                                                             2-methyl-5-                                                                           1:1.10                                                                              "      "       8:1   20                                            amino phenol                                          60 Monohydrate of 3-chloro-4-amino-N-methyl-                                                            2,6-dimeth-                                                                           1:1  Acetone-water                                                                         Ammonium                                                                               2:1   5                       aniline dihydrochloride                                                                              yl-5-              persulfate                                                  acetylamino                                                                    phenol                                                61 Monohydrate of 3-chloro-4-amino-N-methyl-                                                            2,6-dimeth-                                                                           1:1  "      "       1:1   5                       aniline dihydrochloride                                                                              yl-5-amino                                                                     phenol                                                                         hydrochlor-                                                                    ide                                                   62 Monohydrate of 3-chloro-4-amino-N-methyl-                                                            2-methyl-6-                                                                           1:1  "      "       1:1   5                       aniline dihydrochloride                                                                              amino phenol                                          63 Monohydrate of 3-chloro-4-amino-N-methyl-                                                            2-methyl-5-                                                                           1:0.65                                                                              "      "       2:1   5                       aniline dihydrochloride                                                                              acetylamino                                                                    phenol                                                64 Dihydrate of 2-methoxy-4-amino-N-methyl-                                                             2,6--dimethyl-                                                                        1:1  "      "       1:1   0                       aniline sulfate       5-acetyl-                                                                      amino phenol                                          65 3-chloro-4-amino-N-methylaniline dihydro-                                                            2-methyl-5-                                                                           1:1  Ethanol-water                                                                         "       1:1   0                       chloride              N-β-hydroxy-                                                              ethylamino                                                                     phenol                                                66 3-methoxy-4-amino-N-methylaniline dihy-                                                              2,6-dimethyl                                                                          1:1  Acetone-water                                                                         "       2:1   0                       drochloride           phenol                                                67 3-methoxy-4-amino-N-methylaniline dihy-                                                              2,6-dimethy-                                                                          1:0.85                                                                              "      "       1.75:1                                                                               0                       drochloride           yl-5-amino-                                                                    phenol hy-                                                                     drochloride                                           68 Monohydrate of 3-methyl-4-amino-                                                                     2-methyl-                                                                             1:1  Acetone-water                                                                         Ammonium                                                                               2:1   0                       N-methylaniline dihydrochloride                                                                      5-amino            persulfate                                                  phenol                                                69 Monohydrate of 3-methyl-4-amino-N-methyl-                                                            2,6-di-                                                                               1:1  "      "       2:1   5                       aniline dihydrochloride                                                                              methyl-5-                                                                      amino phenol                                                                   hydro-                                                                         chloride                                              70 3-chloro-4-amino-N-methylaniline dihydro-                                                            2,6-di-                                                                               1:1  "      "       2:1   5                       chloride              methyl                                                                         phenol                                                71 Monohydrate of 3-methyl-4-amino-N-methyl-                                                            2-methyl-                                                                             1:1  "      "       1:1   5                       aniline dihydrochloride                                                                              5-acetyl-                                                                      amino phenol                                          72 2-methyl-4-amino-N-methylaniline sulfate                                                             2,6-di-                                                                               1:1  "      "       1:1   5                                             methyl-5-                                                                      amino phenol                                                                   hydro-                                                                         chloride                                              73   "                   2-methyl-5-                                                                           1:1  "      "       2:1   10                                            acetylamino                                                                    phenol                                                74    "                  2-methyl-5-                                                                           1:1  "      "       2:1   10                                            amino phenol                                          75 4-amino-N-methylaniline dihydrochloride                                                              2-methyl-5-                                                                           1:1  "      "       1:1   0                                             acetylamino                                                                    phenol                                                76 2-methoxy-4-amino-N-methylaniline sulfate                                                            2-methyl-5-                                                                           1:1  Acetone-water                                                                         Ammonium                                                                               2:1   0                                             carbethoxy-        persulfate                                                  amino phenol                                          77 2-chloro-4-amino-N-methylaniline sulfate                                                             2-methyl-5-                                                                           1:1  Propanol-water                                                                        "       2:1   0                                             ureido                                                                         phenol                                                78 2-chloro-4-amino-N-β-hydroxyethylaniline                                                        2,6-dimethyl                                                                          1:1  Acetone-water                                                                         "       2:1   0                       sulfate               3-ureido                                                                       phenol                                                79   "                   3-ureido                                                                              1:1  "      "       2:1   0                                             phenol                                                80   "                   3-acetyl-                                                                             1:1  Isopropanol-                                                                          "       2:1   0                                             amino phenol                                                                               water                                     81   "                   2-methyl-5-                                                                           1:1  "      "       2:1   0                                             acetylamino                                                                    phenol                                                82   "                   2-methyl-5-                                                                           1:1  "      "       2:1   0-5                                           ureido                                                                         phenol                                                83 4-amino N-methylaniline dihydrochloride                                                              2-methyl 5-                                                                           1:1  Acetone-water                                                                         "       2:1   0                                             carbamylme-                                                                    thylamino                                                                      phenol                                                84 3-methyl-4-amino-N-methylaniline dihy-                                                                 "    1:1  "      "       2:1   0                       drochloride                                                                 85 2-methyl-4-amino-N-methylaniline dihy-                                                               "      1:1  "      "       2:1   0                       drochloride                                                                 86 2-chloro-4-amino-N-(acetylaminoethyl)                                                                2-methyl 5-                                                                           1:1  Acetone-water                                                                         Ammonium                                                                               2:1   0-5                     aniline sulfate       carbamylme-        persulfate                                                  thylamino                                                                      phenol                                                87 2-chloro-4-amino-N-mesylaminoethyl-                                                                    "    1:1  "      "       2:1   5                    aniline sulfate                                                                88 4-amino-N-β-hydroxyethylaniline sulfate                                                         "      1:1  "      "       2:1   0                    89 2-methyl-4-amino-N-mesylaminoethylaniline                                                            "      1:1  "      "       2:1   5                       sulfate                                                                     90 2-chloro-4-amino-N-methylaniline sulfate                                                             "      1:1  "      "       2:1   0                    91 2-chloro-4-amino-N-(mesylaminoethyl)                                                                 2-methyl-5-                                                                           1:1  "      "       2:1   0                       aniline sulfate       ureido                                                                         phenol                                                92 2-chloro-4-amino-N-(mesylaminoethyl)                                                                 3-ureido                                                                              1:1  "      "       2:1   5                       aniline sulfate       phenol                                                93 2-chloro-4-amino-N-(methylaniline sulfate)                                                           3-acetyl-                                                                             1:1  "      "       2:1   5                                             amino phenol                                          94 2-methyl-4-amino N-ethylaniline sulfate                                                              2-methyl-5-                                                                           1:1  "      "       2:1   5                                             acetylamino                                                                    phenol                                                95 2-chloro-4-amino-N-β-hydroxy-ethylaniline                                                       2,6-dimeth-                                                                           1:1  "      "       1:1   0                       sulfate               yl-3-acetyl-                                                                   amino phenol                                          96 2-chloro-4-amino-N-methylaniline sulfate                                                             2,6-dimethy-                                                                          1:1  "      "       2:1   5                                             yl-3-ureido                                                                    phenol                                                97 2-chloro-4-amino-N-β-hydroxyethylaniline                                                        2-methyl-5-                                                                           1:1  Acetone-water                                                                         Ammonium                                                                               2:1   0                       sulfate               N-carbamyl-        persulfate                                                  methylamino                                                                    phenol                                                98 2-chloro-4-amino-N-mesylaminoethylaniline                                                            3-acetyl-                                                                             1:1  "      "       2:1   5                       sulfate               amino phenol                                          99 2-chloro-4-amino-N-methylaniline sulfate                                                             3-ureido                                                                              1:1  "      "             5                                             phenol                                                __________________________________________________________________________

                                      TABLE III                                    __________________________________________________________________________     (11)                                                                              (12)  (13)                                                                               (14)    (15) (16)                                                                              (17)                                                                              (18)   (19)                                                                              (20)                                                                               (21) (22)                        EX.                                                                               DYE       POLYMER            ALCOHOL                                        NO.                                                                               Ex.No.                                                                               Wt.%                                                                               Type    M.W. (cps)                                                                             %  Type   %  ph  Hair Color                       __________________________________________________________________________                                                        Achieved                    M 1  10  0.5 VA/CA 90/10                                                                              10,000  2  Ethanol                                                                               50 7.8 B 95 (1)                                                                            violine                   M 2   4  0.1 "         10,000  1  "      36 8.1 D (2)                                                                               silvery glycine           M 3   5  0.05                                                                               PVP       40,000  2  Isopropanol                                                                           25 9   D    parme                     M 4  12  0.008                                                                              VA/CA 90/10                                                                              10,000  2  Ethanol                                                                               50 8.1 D    pale pearly rose                                                               mauve                     M 5  15  0.025                                                                              VP/VA 30/70                                                                              160,000 2  "      40 8.8 D    emerald green             M 6  19  0.004                                                                              VA/CA 90/10                                                                              25,000  1  "      36 8.4 D    light pink blonde         M 7   2  0.05                                                                               PVP       160,000 2  Isopropanol                                                                           25 9   D    pearly mauve              M 8  17  0.01                                                                               VP/VA 60/40    4  2  "      35 9.6 D    very light silver         M 9   1  0.05                                                                               VA/CA 90/10                                                                              25,000  1  Ethanol                                                                               20 9.5 D    pale silvery mauve        M 10 18  0.1 VP/CA 30/70                                                                              160,000 2  "      40 10.2                                                                               D    pearly turquoise                                                               blue                      M 11  5  0.002                                                                              "         "       2  "      40 5.7 D    light pink blond          M 12 18  0.1 "         "       2  "      40 10.2                                                                               B 95 silvery eucalyptus                                                             green                     M 13 14  0.1 VA/CA 90/10                                                                              25,000  1  "      36 8.5 D    very luminous                                                                  gentian                   M 14 10  0.2 "         25,000  2  "      50 7.4 D    purple                    M 15  3  0.1 VP/VA 60/40    3.3                                                                               2  Isopropanol                                                                           35 9.8 B 95 beige grey with                                                                violet                                                                         glints                    M 16 16  0.02                                                                               VP/VA 70/30                                                                              40,000  3  Ethanol                                                                               25 8.7 D    ice-blue                  M 17 10  0.002                                                                              "         "       3  "      25 10.1                                                                               "    pearly pale pink          M 18  9  0.015                                                                              VP/VA 30/70                                                                              160,000 2  "      40 9.3 "    pearly light blue         M 19 13  0.013                                                                              VP/VA 60/40    3.7                                                                               2  Isopropanol                                                                           35 9.3 "    light turquoise                                                                blue                      M 20 6   0.05                                                                               MM/StM/DEM     8  2.5                                                                               Ethanol                                                                               30 8   "    deep violet pink                       20/23/57                                                          M 21 18  0.1 VP/VA 30/70                                                                              160,000 2  "      40 10.2                                                                               "    deep chestnut with                                                             bronze glints                  14  0.05                                                                  M 22 10  0.1 VA/CA 90/10                                                                              50,000  2  "      50 6.7 D    deep violet                    C.sub.1 (3)                                                                        0.08                                                                       14  0.05                                                                  M 23 10  0.002                                                                              VA/CA 90/10                                                                              70,000  2  "      50 7.5 D    golden light                                                                   chestnut                                                                       with violet glints             C.sub.1 (3)                                                                        0.15                                                                       C.sub.2 (4)                                                                        0.12                                                                  M 24  7  0.2 MM/StM/DEM     12 2.5                                                                               "      30 10.5                                                                               B 95 tin grey with light                                                            violet glints             M 25 28  6.09                                                                               VA/CA 90/10                                                                              25,000  2  "      50 6.3 D    silvery glycine           M 26 30  0.09                                                                               VP/VA 60/40    4  2  Isopropanol                                                                           35 8.1 D    silvery blue grey         M 27 20  0.009                                                                              VP/VA 70/30                                                                              40,000  3  Ethanol                                                                               25 8.5 D    pearly light green        M 28 34  0.02                                                                               VP/VA 60/40    4  2  Isopropanol                                                                           35 9.4 D    pearly light blue         M 29 32  0.02                                                                               "              3.3                                                                               2  "      35 5.5 D    light parme               M 30 31  0.05                                                                               "              3.7                                                                               2  "      35 9   D    silvery grey with                                                              mauve                                                                          glints                    M 31 23  0.015                                                                              PVP       360,000 2  "      25 8.9 D    light green with                                                               golden                                                                         glints                    M 32 33  0.025                                                                              VA/CA 90/10                                                                              50,000  1  Ethanol                                                                               36 5.5 D    pearly light blue         M 33 25  0.5 "         50,000  2  "      50 10.1                                                                               B 95 metallic grey             M 34 35  0.05                                                                               "         70,000  1  "      36 9.2 D    silvery pale mauve        M 35 21  0.05                                                                               "         50,000  2  "      50 7   D    silvery blue grey         M 36 36  0.06                                                                               "         "       2  "      50 8.8 D    pearly grey               M 37 37  0.065                                                                              VP/CA 60/40    3.3                                                                               2  Isopropanol                                                                           35 9.3 B 95 dark blue grey            M 38 27  0.05                                                                               MM/StM/DEM(5)  2.5                                                                               2.5                                                                               Ethanol                                                                               30 10.3                                                                               D    pink beige grey           M 39 24  0.1 VA/CA 90/10                                                                              50,000  2  "      50 6.4 D    very luminous deep                                                             violet                    M 40 26  0.033                                                                              VP/CA 70/30                                                                              40,000  3  "      25 6.7 D    pearly light blue         M 41 22  0.09                                                                               VP/CA 30/70                                                                              160,000 2  "      40 9.7 B 95 metallic grey             M 42 21  0.002                                                                              PVP       360,000 2  Isopropanol                                                                           25 10.3                                                                               D    very light silver                                                              with blue                                                                      glints                    M 43 29  0.045                                                                              MM/StM/DEM(5)  8  2.5                                                                               Ethanol                                                                               30 9   D    tamarisk pink              (1) B 95 = 95% natural white hair                                              (2) D = bleached hair                                                          3 C.sub.1 = N[4'-hydroxy)-phenyl]-2,6-dimethyl benzoquinoneimine               (4) C.sub.2 = 4-nitro-N,N-di-β-hydroxyethylaniline                        (5) Terpolymer of methyl methacrylate (20%)-stearyl methacrylate (23%)         dimethylaminoethyl methacrylate (57%) quaternized with dimethyl sulfate        and having a viscosity of 8-12 cps, at 5% in dimethylformamide and at the      boiling temperature of ether.                                            

    M 44 39  0.3 PVP     40,000 2 Isopropanol                                                                           25                                                                               5.5                                                                               D     deep royal blue                M 45 38  0.1 VA/CA 90/10                                                                            70,000 1 Ethanol                                                                               36                                                                               9  B 95  silvery grey with mauve                                                        glints                              36  0.1                                                                   M 46 22  0.2 VA/CA 90/10                                                                            "      2 "      50                                                                               7  B 95  steel grey                        C.sub.3 (5)                                                                      0.02                                                                           C.sub.4 (6)                                                                        0.03                                                                  M 47 57  0.25                                                                               VP/VA 60/40  3.7                                                                              2 Isopropanol                                                                           35                                                                               8.5                                                                               D     silvery pale violet            M 48 60  0.1 "            4 2 "      35                                                                               5.5                                                                               D     silvery grey with light                                                        mauve glints                   M 49 69  0.3 VA/CA 90/10                                                                            45,000 2 Ethanol                                                                               50                                                                               5  D     violine                        M 50 99  0.35                                                                               "       "      2 "      50                                                                               7  B 95  metallic grey                  M 51 94  0.1 "       "      2 "      50                                                                               6.5                                                                               D     very light pearly blue         M 52 66  0.35                                                                               "       "      2 "      50                                                                               7  D     royal blue                     M 53 92  0.15                                                                               VP/VA 70/30                                                                            40,000 3 "      25                                                                               8  D     pearly pink beige              M 54 91  0.15                                                                               VA/CA 90/10                                                                            50,000 1 "      36                                                                               7  D     lilac                          M 55 65  0.3 "       "      2 "      50                                                                               9.5                                                                               D     violet beige                   M 56 75  0.1 VP/VA 60/40  4 2 Isopropanol                                                                           35                                                                               5  D     silvery blue                   M 57 63  0.05                                                                               "            4 2 "      35                                                                               10.5                                                                              D     cyclamen pink                  M 58 59  0.035                                                                              VP/VA 60/40  3.5                                                                              2 Isopropanol                                                                           35                                                                               6  D     salmon pink                    M 59 53  0.05                                                                               VP/VA 30/70                                                                            160,000                                                                               2 Ethanol                                                                               40                                                                               6  D     beige shaded mauve             M 60 67  0.09                                                                               "       "      2 "      40                                                                               8.5                                                                               D     pearly glycine                 M 61 61  0.07                                                                               VP/VA 60/40  3.7                                                                              2 Isopropanol                                                                           35                                                                               9.5                                                                               D     pearly pale pink               M 62 71  0.03                                                                               VP/VA 30/70                                                                            160,000                                                                               2 Ethanol                                                                               40                                                                               8.5                                                                               D     pearly myosotis blue           M 63 76  0.05                                                                               "       "      2 "      40                                                                               10 D     light blue grey                M 64 72  0.2 "       "      2 "      40                                                                               4.5                                                                               D     purple                         M 65 73  0.1 "       "      2 "      40                                                                               5  D     silvery lavender blue          M 66 88  0.2 VP/VA 70/30                                                                            40,000 3 "      20                                                                               8.5                                                                               D     silvery grey violet                 26  0.15                                                                  M 67 62  0.025                                                                              VA/CA 90/10                                                                            70,000 1 "      35                                                                               7  D     pink beige                     M 68 64  0.15                                                                               "       10,000 2 "      50                                                                               7  D     myosotis blue                  M 69 68  0.13                                                                               "       50,000 1 "      36                                                                               4.5                                                                               D     violet pink                    M 70 58  0.05                                                                               "       "      2 "      50                                                                               8.5                                                                               D     very luminous salmon                                                           pink                           M 71 51  0.1 "       "      1 "      36                                                                               7  D     silvery grey blue              M 72 89  0.1 VP/VA 60/40  3.7                                                                              2 Isopropanol                                                                           35                                                                               4  D     silvery glycine                M 73 88  0.1 PVP     40,000 2 "      25                                                                               9  B 95  metallic grey with mauve                                                       glints                         M 74 87  0.05                                                                               VP/VA 30/70                                                                            160,000                                                                               2 Ethanol                                                                               40                                                                               8.5                                                                               D     golden pale pink               M 75 86  0.075                                                                              VP/VA 70/30                                                                            40,000 3 "      25                                                                               6.5                                                                               D     eglatine                       M 76 85  0.05                                                                               VP/VA 60/40  4 2 Isopropanol                                                                           35                                                                               4 .sup.[                                                                          D     glycine                        M 77 98  0.1 VP/VA 30/70                                                                            160,000                                                                               2 Ethanol                                                                               40                                                                               7  D     light silver                   M 78 56  0.2 VA/CA 90/10                                                                            70,000 1 "      36                                                                               9  D     mauve                          M 79 50  0.2 "       50,000 1 "      36                                                                               5.5                                                                               D     violet                         M 80 81  0.2 VP/VA 30/70                                                                            160,000                                                                               2 "      40                                                                               4  D     light grey with mauve                                                          glints                         M 81 79  0.075                                                                              VA/CA 90/10                                                                            50,000 1 "      50                                                                               7  D     light silery grey shaded                                                       mauve                          M 82 54  0.1 "       50,000 1 "      50                                                                               7  D     violet blue                    M 83 45  0.1 "       70,000 1 "      36                                                                               8  D     silvery myosotis blue          M 84 46  0.1 "       70,000 1 "      36                                                                               9  D     pearly mauve                   M 85  8  0.2 VP/VA 30/70                                                                            160,000                                                                               2 "      40                                                                               8  D     tamarisk pink                  M 86 42  0.1 VA/CA 90/10                                                                            70,000 2 "      50                                                                               6.5                                                                               D     silvery blue grey              M 87 44  0.3 "       70,000 2 "      50                                                                               6  D     lavender                       __________________________________________________________________________                                                     blue                            (5) C.sub.3 = Nitro-ortho p-phenylenediamine                                   (6) C.sub.4 = 1-γ-amino propylamino anthraquinone                  

                                      TABLE IV                                     __________________________________________________________________________     (31)                                                                              (32)  (33)                                                                               (34)   (35)                                                                              (36)  (37)                                                                              (38)  (39)                                                                               (40)                                                                               (41)  (42)                                    Surface active                                                    DYE          agent     SOLVENT  OTHER ADJUVANTS                                EX.                 wt.      wt.      wt.                                      N0.                                                                               EX. NO.                                                                              Wt. %                                                                              Type   %  Type  %  Type  %   pH  Hair  Color                      __________________________________________________________________________                                                         achieved                   T 1                                                                                1    0.53          Isopropanol                                                                          40           11  D (10)                                                                               silver with                                                                    mauve glints               T 2                                                                                2    0.04          MEDG(1)                                                                               5           9   D     silvery mauve grey                                Ethanol                                                                              25                                                T 3                                                                               15    0.077         Ethanol                                                                              23 CMC (2)                                                                               3.9                                                                               10.4                                                                               D     emerald green              T 4                                                                                5        AL 10.50E                                                                             5  Butylglycol                                                                           5           6   D     light pink blond                        (3)                                                               T 5                                                                               16    0.6                                                                       2    0.5                                                                      Cl (4)                                                                               0.05                                                                                 "    20                     8.5                                                                               D     pink beige                    C2 (5)                                                                               0.07                                                                  T 6                                                                                3    0.30                                                                               LSS 19 (6)                                                                            20          EDTA (7)                                                                             2   10.6                                                                               D     silvery grey with                                                              blue glints                T 7                                                                                9    0.06          Ethanol                                                                              20 CMC   4   8   D     pearly light                                                                   turquoise blue             T 8                                                                               18    0.2 NP 40E (8)                                                                            10                                                                      NP 90E (9)                                                                            10                     5.6                                                                               395(11)                                                                              vervain                    T 9                                                                               10    0.1 ALS (12)                                                                              10                    9.7 D     pearly light                                                                   pink                       T 10                                                                              16    0.1   "    10                    10.5                                                                               D     pearly light green         T 11                                                                               6    0.33          Ethanol                                                                              30 CMC   3   10.5                                                                               B 95  silvery violet             T 12                                                                               4    0.4 AL 10.50E                                                                             20                    10    "   eucalyptus green           T 13                                                                              15    0.1 LSS 19 20          EDTA  2   10.5                                                                               D     mahogany                      C3 (14)                                                                              0.08                                                                     C4 (15)                                                                              0.10                                                                     C5 (16)                                                                              0.04                                                                  T 14                                                                              11    0.025         Isopropanol                                                                          50 "Carbopol                                                                      934" (17)                                                                             2.38                                                                              6   D     light green                T 15                                                                              27    0.07                                                                               LSS 19 20          EDTA  0.2 10.7                                                                               D     light beige grey           T 16                                                                              23    1   NP 90E 10   "   15            5.5                                                                               B 95  petroleum blue             T 17                                                                              20    0.7 DFAC (13)                                                                             7.5                                                                               Ethanol                                                                              25           7     "   eucalyptus green           T 18                                                                              32    0.1             "   20           10.5                                                                               D     pearly pink beige                                 MEDG  10                                                T 19                                                                              23    0.30                                                                               NP 40E 8.5                   9   B 95  light chestnut with           20    0.35                                                                               NP 90E 8.5                                                                               Ethanol                                                                              15                     copper glints                 C6 (18)                                                                              0.03                                                                     C7 (19)                                                                              0.1                                                                   T 20                                                                              24    0.4           Ethanol                                                                              40           9   D     deep violet blue           T 21                                                                              37    1.1             "   45            9.5                                                                               D     myosotis blue              T 22                                                                              33    0.8             "   20 CMC   4    5.5                                                                               D     silvery light blue         T 23                                                                              37    0.3                                                                      24    0.2             "   40           10.5                                                                               B 95  silvery mauve grey            C2 (5)                                                                               0.09                                                                     C8 (20)                                                                              0.05                                                                  T 24                                                                              26    0.65            "   33 "Carbopol                                                                            3   10  D     light emerald green                                        934" (17)                                      T 25                                                                              25    0.22                                                                               NP 90E 10 Butylglycol                                                                           5            5.5                                                                               D     platinum with light                                                            blue glints                T 26                                                                              34    2   DFAC (13)                                                                             6.5                                                                               Ethanol                                                                              35           10.5                                                                               D     pearly light                                                                   turquoise blue             T 27                                                                              43    0.4 AL 10.50E                                                                              5 Butylglycol                                                                           5           7   D     very silvery pale                       (3)                              blue                             T 28                                                                              40    0.25                                                                               DFAC (13)                                                                             10                     9.5                                                                               D     pearly pastel blue         T 29                                                                              48    0.2 ALS (12)                                                                              10                    9   D     ice blue                   T 30                                                                              49    0.4                    "Carbopol                                                                             4.76                                                                               9.5                                                                               D     pearly pastel blue                                         934" (17)                                      T 31                                                                              47    0.4 LSS 19 (6)                                                                            20          EDTA   0.2                                                                               12  D     light bluish silver        T 32                                                                              41    0.05                   CMC (2)                                                                              5   10  D     very light pearly                                                              blue                       T 33                                                                              90    0.5 Al 10.50E                                                                              5                    9   D     eglantine pink                          (3)                                                               T 34                                                                              95    0.35                                                                               LSS 19 (6)                                                                            20          EDTA (7)                                                                              0.2                                                                               10  D     light silver grey          T 35                                                                              93    0.3                    CMC (2)                                                                              5   9   D     light blue grey            T 36                                                                              96    0.3           MEDG (1)                                                                             10           5   D     silvery mauve              T 37                                                                              97    0.4 DFAC (13)                                                                             10                    9   D     very light pink                                                                blond                      T 38                                                                              78    0.5 LSS 19(6)                                                                             20          EDTA (7)                                                                              0.2                                                                               10  D     mauve                      T 39                                                                              52    0.15          Ethanol                                                                              25           9   D     light turquoise                                                                blue                       T 40                                                                              70    0.6 "      20            "    0.2                                                                               11  D     pearly light                                                                   beige grey                 T 41                                                                              84    0.35            "   20 "Carbopol                                                                             3.6                                                                               10  D     silvery pale                                               934" (17)           mauve                      T 42                                                                              83    0.35                                                                               ALS (12)                                                                               5                 9.2                                                                               D   light silver grey                                                                    with mauve glints          T 43                                                                              74    0.6 DFAC (6)                                                                               2   "   30           10.5                                                                               B 95  metallic grey                                                                  with mauve glints          T 44                                                                              55    0.8 NP 40E (8)                                                                             8   "    2           11  D     light silver grey                       NP 90E (9)                                                                             8                                                         T 45                                                                              80    0.4 Al 10.50E  5                                                                          Butylgly-                                                                          5             9   D   silvery light blue                            (3)       col                          grey                       T 46                                                                              77    0.5 AL10.50E(3)                                                                           20                    4   D     pearly light               T 47                                                                              82    0.2           Propylene                                                                             5 CMC (2)                                                                              4   8   D     light pink ash                                    glycol                 beige                            T 48                                                                              93    0.2           Ethanol                                                                              50   "    2.5                                                                               10  B 95  metallic grey                                                                  shaded violet                 87    0.5                                                                      35    0.1                                                                   __________________________________________________________________________      .sup.(1) MEDG = monomethyl ether of diethyleneglycol                           .sup.(2) CMC = Carboxymethylcellulose                                          .sup.(3) Al 10.5 OE = laurylalcohol oxyethylenated with 10.5 moles of          ethylene oxide                                                                 .sup.(4) C1 = 2-methoxy-4-nitro-β-hydroxyethylaniline                     .sup.(5) C2 = 1-γ-aminopropylamino anthraquinone                         .sup.(6) LSS 19 = mixture consisting of 19% laurylalcohol oxyethylenated       with 2 moles of ethylene oxide and 81% of the sodium sulfate salt of the       same oxyethylenated alcohol                                                    .sup.(7) EDTA = ethylene diamine tetra-acetic acid                             .sup.(8) NP 40E = Nonylphenol oxyethylenated with 4 moles of ethylene          oxide                                                                          .sup.(9) NP 90E = Nonylphenol oxyethylenated with 9 moles of ethylene          oxide                                                                          .sup.(10) D = bleached hair                                                    .sup.(11) B 95 = 95% naturally white hair                                      .sup.(12) ALS = ammonium laurylsulfate                                         .sup.(13) DFAC = diethanolamides of fatty acids of coprah                      .sup.(14) C3 = N-[(4'-hydroxy)phenyl]-2,6-dimethylbenzoquinoneimine            .sup.(15) C4 = N-[(4'-amino)phenyl] 2-methyl-5-aminobenzoquinoneimine          .sup.(16) C4 = Nitroorthophenylenediamine                                      .sup.(17) "Carbopol 934" = Polymer of acrylic acid having a molecular          weight between 2-3 million                                                     .sup.(18) C6 = N-[(4'-ethylamino)phenyl]-2-methyl 5-acetylamino                .sup.(19) C7 = nitroparaphenylenediamine                                       .sup.(20) C8 = 3-nitro-4(β-hydroxyethyl) amino anisole               

We claim:
 1. A composition for dyeing keratin fibers which comprises a dyeing effective amount of an indoaniline compound of the formula ##STR9## or a tautomeric form thereof wherein R₁ and R₄ each independently represent a member selected from the group consisting of hydrogen, halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, acetylamino and ureido,R₂ and R₃ each independently represent a member selected from the group consisting of hydrogen, halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, amino, N-alkylamino, N-(hydroxyalkyl)-amino, N-(carbamylalkyl)-amino, acetylamino and ureido, each of said alkyl moieties containing 1 to 6 carbon atoms, R₅ and R₆ each independently represent a member selected from the group consisting of hydrogen, halogen, alkyl having 1 to 6 carbon atoms and alkoxy having 1 to 6 carbon atoms with the proviso that when R₅ and R₆ are both other than hydrogen at least one is in a meta-position relative to the NHR₇ ; and R₇ represents a member selected from the group consisting of alkyl, hydroxyalkyl, acetylaminoalkyl, mesylaminoalkyl, carbamylalkyl, aminoalkyl and morpholinoalkyl, each of said alkyl moieties containing 1 to 6 carbon atoms and a compatible vehicle.
 2. The composition according to claim 1 which contains from 0.001 to 2% by weight of said compound.
 3. The composition according to claim 1 wherein the vehicle is an aqueous solution, a cream or a gel.
 4. The composition according to claim 2, having a pH from 5 to
 11. 5. The composition according to claim 4, having a pH from 7 to
 9. 6. The composition according to claim 1, which also contains another direct hair dye.
 7. The composition according to claim 6, wherein said direct hair dye is selected from the group consisting of nitrobenzene, azo, anthraquinone, indamine, indophenol and another indoaniline dye.
 8. The composition according to claim 1 which also contains a member selected from the group consisting of a glycol and a wetting agent.
 9. The composition according to claim 1 wherein the vehicle is an aqueous-alcoholic solution and also contains a cosmetic film-forming resin.
 10. The composition according to claim 9, wherein the alcohol is a low molecular weight alcohol.
 11. The composition according to claim 10, wherein said alcohol is selected from the group consisting of ethanol and isopropanol.
 12. The composition according to claim 10, which contains 20 to 70% by weight of said alcohol.
 13. The composition according to claim 9 which contains 1 to 3% by weight of said cosmetic film-forming resin.
 14. The composition according to claim 9 wherein said cosmetic film-forming resin is selected from the group consisting of polyvinylpyrrolidone; copolymer of vinylpyrrolidone and vinyl acetate; copolymer of vinyl acetate and crotonic acid; copolymer of maleic anhydride and butyl vinyl ether; copolymer of methyl vinyl ether and maleic anhydride and the ethyl, isopropyl and butyl esters thereof; and a terpolymer of methyl methacrylate, stearyl methacrylate and dimethylaminoethyl methacrylate quaternized by dimethyl sulphate.
 15. A process for dyeing living human hair comprising impregnating said hair with a composition as defined in claim 1 for 5 to 30 minutes, rinsing said hair and optionally washing said hair with a shampoo and drying said hair.
 16. A process for coloring and wavesetting living human hair comprising applying to said hair which has been washed and rinsed a composition as defined in claim 9, constraining the hair in a deformed state and drying said hair. 